12-alkylquinoxalophenoxazine compounds and cations



United States Patent 3,485,832 1Z-ALKYLQUINOXALOPHENOXAZINE COMPOUNDS AND CATIONS Raymond C. Harris and James M. Straley, Kingsport,

Tenn, assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey No Drawing. Filed Mar. 29, 1967, Ser. No. 626,689 lint. Cl. C07d 99/00; C091) 19/00; D06p US. Cl. 260244 7 Claims ABSTRACT OF THE DISCLOSURE Novel 12-alkylquinoxalophenoxazine compounds and cations prepared by reacting an N-alkyl-3-hydroxy-2-phenazinone with an o-aminophenol are useful as dyes for acrylic, modacrylic, and acid-modified polyester textile materials.

This invention relates to novel chemical compounds and cations and to the use of such compounds and cations as dyes for acrylic, modacrylic and acid-modified polyester textile fibers, yarns and fabrics.

The compounds and cations of the invention have the general formula B it /N X/ \Y a N 0 wherein R represents an alkyl group, R represents lower alkyl or benzyl, n represents 0 or 1, and X and Y each represent an o-phenylene or an o-naphthylene group.

The compounds and cations of the invention give blue to violet dyeings, which exhibit excellent fastness properties, on acrylic, modacrylic, and acid'modified textile materials when applied thereto according to conventional dyeing procedures.

The alkyl group represented by R can contain up to about 12 carbon atoms which can be branch or straight chain, substituted or unsubstituted alkyl. Typical unsubstituted alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, 2'ethyl hexyl, octyl, etc. Illustrative of the substituents that can be present on the alkyl group represented by R are hydroxy, alkoxy, nitro, cyano, lower alkanoyloxy, lower alkoxycarbonyl, halo, e.g. chloro, bromo, fluoro, lower alkanoylamido, carbamoyl, lower alkyl substituted carbamoyl, lower alkyl substituted carbamoyloxy, phenyl substituted carbamoyloxy, lower alkylsulfonyl, lower alkoxycarbonyloxy, lower dicarboxylic acid imido, phenyl phenoxy, lower alkylsulfonamido, etc.

Preferably, the alkyl groups represented by R are those which contain up to about four carbon atoms. Examples of the preferred alkyl groups include methyl, ethyl, propyl, isopropyl, and butyl. Examples of preferred substituted alkyl groups represented by R are Z-hydroxyethyl, 2,3-dihydroxypropyl, 2-methoxyethyl, Z-ethoxyethyl, Z-nitroethyl, Z-cyanoethyl, 2-ethoxyethyl, 2-acetoxyethyl, 3-ethoxycarbonylpropyl, Z-chloroethyl, 3-chloropropyl, 2-bromoethyl, trifiuoromethyl, 3-chloro-2-hydroxypropyl, Z-acetamidoethyl, Z-carbamoylethyl, 2-N-propylcarbamoylethyl,

'ice

2 N,N-dimethylcarbamoylethyl, 2-N-ethylcarbamoyloxyethyl, 3-N-phenylcarbamoyloxyethyl, Z-methylsulfonylethyl, 2-ethylcarbonyldioxyethyl, 2-succinimid0ethyl, benzyl, phenoxymethyl, Z-methylsulfonamidoethyl, sulfamoyl, etc.

Methyl, ethyl, propyl, isopropyl, butyl, etc. are typical of the lower alkyl groups represented by R The o-phenylene groups which each of X and Y can represent can be unsubstituted or substituted, for example, with lower alkyl groups, lower alkoxy groups, halogen, lower alkanoylamino, nitro, cyano, lower alkylsulfonyl, carbamoyl, lower alkyl substituted carbamoyl, hydroxyl, aryl, alkanoyl, benzamido, amino, lower alkyl substituted amino, arylamino, lower alkoxycarbonyl, sulfamoyl, lower alkyl substituted sulfamoyl, lower alkylsulfonamide, dicarboxylic acid imido, thiocyanato, lower alkylthio, etc. Illustrative of the groups represented by X and Y are 0- phenylene, 1,2-naphthylene, 2,3-naphthylene, 3,4-na hthylene, 4-trifiuoromethyl-Z-phenylene, 4-ehloro-5-methyl-2- phenylene, 4-sulfamoyl-2-phenylene, 4-nitro-2-phenylene, 4 methylsulfonyl 5 methyl-Z-phenylene, 4-methoxy-2- phenylene, 3-acetyl-2-phenylene, etc.

Examples of the lower alkyl groups that can be present on the o-phenylene groups represented by X and Y are those described above in the definition of R. Examples of the alkoxy groups are methoxy, ethoxy, propoxy, butoxy, etc. Chlorine and bromine are illustrative of the halogen atoms that can be present on the groups represented by X and Y. Typical lower alkanoyl and alkanoylamino groups include acetyl, propionyl, butyryl, acetamido, propionamido, butyramido, etc. Examples of the lower alkylsulfonyl and lower alkylsulfonamido, groups which can be present on the o-phenylene groups X and Y include methylsulfonyl, ethylsulfonyl, butylsulfonyl, methylsulfonamido, ethylsulfonarnido, propylsulfonamido, butylsulfonamido, etc.

N-methylsulfamoyl, N-propylsulfamoyl, N,N-diethylsulfamoyl, N-ethylcarbamoyl, N,N-dibutylcarbamoyl, and, N,N-dimethylcarbamoyl are typical substituted sulfamoyl and carbamoyl groups that can be present on the o-phenylene groups represented by X and Y. Illustrative of the alkoxycarbonyl groups are methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc. Dimethylamino, diethylamino, and dibutylamino are examples of the substituted amino groups. Anilino is typical of the arylamino groups. Succinimido, glutarimido, phthalimido, and maleimido are typical dicarboxylic acid imido groups. Methylthio, ethylthio, propylthio, isopropylthio, and butylthio are illustrative of the alkylthio groups that can be present on the o-phenylene group X and Y. Phenyl and phenyl substituted with lower alkyl, e.g. p-tolyl, lower alkoxy, e.g., p-anisyl, and halogen, e.g. p-chlorophenyl, are examples of the aryl groups.

Preferably, Y represents o-naphthylene or an o-phenylene group having the formula wherein R R R are the same or difierent and each represents hydrogen, lower alkyl, trifluoromethyl, lower alkoxy, sulfamoyl, lower alkylsulfonyl, halogen, or nitro.

The groups represented by X are preferably a o-naphthylene or an o-phenylene group having the formula wherein R and R are the same or different and each represents hydrogen or a substituent described in the preceding definition of R R and R The novel compounds of the invention are prepared by reacting an N-alkyl-3-hydroxy-2-phenazinone With an o-aminophenol or an o-aminonaphthol according to the following reaction:

The novel cations of the invention are prepared by treating the unquaternized compounds described above with an alkylating agent at elevated temperatures to obtain cations having the formula wherein R and R are defined above, n is l, and Z represents a monovalent acid anion derived from the alkylating agent. Suitable alkylating agents that can be used in preparing the novel cations of the invention are the dialkyl sulfates, the alkyl halides, the aralkyl halides, the alkyl esters of aryl sulfonic acids, etc. Specific alkyating agents include, for example, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, ethyl bromide, ethyl chloride, methyl iodide, benzyl chloride, benzyl bromide, methylp-toluenesulfonate, ethyl-p-toluenesulfonate, and ethyl benzenesulfonate.

The primary color of the novel compounds and cations of the invention is attributable to the conjugation of the molecule R .s N X/ \Y III 0 wherein R, R n, X, and Y are defined above. Thus, the substituents present on the groups represented by R, X,

and Y do not materially affect the primary usefulness of the novel compounds and cations as dyes for the abovementioned textile materials. These substituents function primarily as auxochrome groups to control the shade of the novel compounds and cations.

Although the novel cations of the invention exist in combination with an anion, the cations are described herein and in the appended claims as not being associated with any anion. The anion does not effect the usefulness of the cations as dyes nor does it affect the dye affinity of the cations for the described textile materials. When the compounds are used to dye polyacrylonitrile textile. the anion becomes associated with a positively charged ion derived from the polyacrylonitrile and is removed from the dye cation and polyacrylonitrile textile mate rial, either in the dyebath or in a subsequent Washing of the dyed polyacrylonitrile textile material. Since the cation of a cationic dye is responsible for the color of the cationic dye, the particular anion associated with the cation is not important.

The preparation of the novel compounds and cations of the invention are further described and illustrated in the following examples.

PREPARATION OF THE PHENAZINONES Example A The phenazinones intermediates used in the preparation of the novel compounds of the invention are prepared according to the procedure described in the following reaction.

68 g. (0.5 mole) of n-ethyl-o-phenylenediamine and 70 g. (0.5 mole) of .2,S-dihydroxybenzoquinone are mixed in 1300 ml. of water and ml. of concentrated hydrochloric acid. The mixture is heated to boiling and stirred at reflux temperature for one hour. The reaction mixture is then cooled to room temperature, made basic with 50% sodium hydroxide solution and filtered through a sintered glass funnel. The filtrate is neutralized with acetic acid and filtered. The filter cake is thoroughly washed with water and dried to give a quantitative yield of 10-ethyl-3-hydroxy-2-phenazinone.

'Example B The 10-methyl-3-hydroxy-2-phenazinone is prepared as follows: 61 g. (0.5 m.) of N-methyl-o-phenylenediamine and 70 grams (0.5 m.) of 2,S-dihydroxybenzoquinone are mixed in 1300 cc. of water containing 100 cc. of concentrated hydrochloric acid. The slurry is heated to boiling and stirred under reflux for one hour. The reaction mixture is then cooled to room temperature, made basic with 50% sodium hydroxide solution, and filtered through a sintered glass funnel. The filtrate is neutralized with acetic acid and filtered. The filter cake is thoroughly Washed with Water and dried. Yield=98% of product which is pure enough for use without further treatment.

By replacing the phenylenediamine reactant employed in the above examples with various substituted derivatives of both phenylenediamine and naphthylenediamine, the phenazinones useful in preparing the compounds of the invention can be obtained.

PREPARATION OF THE DYES Example 1 (A) A mixture of 4.8 g. (.02 In.) of 10-ethyl-3-hydroxy-Z-phenazinone, and 2.92 g. (.02 m.) of o-aminophenol hydrochloride is slurried in 25 ml. of 3-picoline and heated slowly to reflux temperature. The solution 15 stirred at 143 C. for 3 /2 hours, removing any Water as formed. The reaction mixture is then chilled and filtered. and the precipitate washed with water. The filter cake is then slurried in dilute caustic soda solution and filtered. The precipitate is thoroughly washed with water and dried at 60 C. The product dyes acrylic fibers dark blue violet shades with excellent fastness to light, washing and alkaline perspiration tests. It has the formula:

I Q O N 0 The compound obtained according to the procedure described in Example 1 can alternatively be prepared according to the following methods.

(B) A slurry of 4.8 g. of -ethyl-3-hydroxy-2-phenazinone, 3 g. of o-aminophenol hydrochloride and ml. of ethylene glycol is slowly heated to 175 C. and stirred for 1% hours at 175-185 C. The reaction mixture is then drowned in 600 ml. of water, made basic with dilute aqueous ammonia and filtered. The product is slurried in dilute caustic solution, filtered and washed with water. The product is identical to that of Example 1.

(C) A slurry of 4.8 g. of l0-ethyl-3-hydroxy-2-phen azinone and 3 g. of o-arninophenol hydrochloride in 100 m1. of water is heated at 175 C. in a stainless steel rocking autoclave for 6 hours. The contents of the autoclave are then made basic with dilute aqueous ammonia and filtered. The filter cake is Washed with water, slurried in dilute caustic soda solution and refiltered. This filter cake is thoroughly washed with water and dried at 60 C. The product is identical to that of Example 1.

Example 2 3.13 g. (.01 mole) of 12-ethyl-12H-quinoxalino[2-31)]- phenoxazine, prepared as in Examiple 1 in 25 ml, of dimethyl sulfate is heated on a steam bath for 1.5 hours. The reaction mixture is drowned in ether and filtered. The precipitate is thoroughly washed with ether and vacuum dried. Yield:4.3 g.

The methosulfate quaternary salt thus formed dyes acrylic fibers such as Acrilan and Orlon bright blue violet shades with excellent light and wash fastness properties.

One gram of the above methosulfate quaternary salt is dissolved in warm water and 3 g. of potassium iodide is added. After cooling to room temperature, the precipitated iodide quaternary is filtered off, washed with water and dried. Dyeings on Orlon are the same shades and have the same fastness properties as the methosulfate quaternary.

Example 3 4.8 g, of 10-ethyl-3-hydroxy-2-phenazinone and 3.91 g. of l-amino-Z-naphthol hydrochloride are slurried in 25 ml. of 3-picoline. The reaction mixture is heated to 143 C. and stirred at gentle reflux for 4 hours removing water as formed. The reaction mixture is then cooled to room temperature and filtered. The filter cake is washed with water, then with a weak aqueous ammonia solution, then thoroughly with water. The product, 14-ethyl-14H-benzo- [j]quinoxaline-[2,3-b]phenoxazine, is a dark powder which dyed acrylic fibers blue. It has the structure:

Example 4 A slurry of 2 g. of 14-ethyl-14H-benzo[j]quinoxalino- [2,3-b]phenoxazine, prepared as described in Example 3 in 25 m1. of dimethyl sulfate is stirred 2 hours at 95 C. The reaction mixture is drowned in diethyl ether. The precipitate is filtered off and thoroughly washed with ether. The quaternary methosulfate dyes acrylic fibers blue shades with excellent fastness properties.

Example 5 2.68 g. of l0-butyl-3-hydroxy-2-phenazinone and 1.77

g. of 2-amino-4-trifiuoromethyl phenol are slurried in 12.5

d o F,

Example 6 A mixture of 4.8 g. of 10-ethyl-3-hydroxy-2-phenazinone, 3.5 g. of 2-amino-4-chloro-5-rnethylphenol, 2.5 ml. of concentrated hydrochloric acid and 25 ml. of ethylene glycol is heated slowly to C. and stirred at 175 C. to C. for 2 hours. The solution is then allowed to cool to approximately 100 C, and drowned in 600 ml. of water. The aqueous slurry is made basic with ammonia, filtered, and the filter cake thoroughly washed with water. The moist cake is then slurried in a 3% sodium hydroxide solution, filtered and washed with hot water until a colorless filtrate was obtained. The product is recrystallized from a 1,4-dioxane-water mixture. Acrylic fibers are dyed in blue-violet shades with the product 2-chloro-12- ethyl 3 methyl- 12H- quinoxalino[2,3-b1phen0xazine, which has the structure:

Example 7 3.64 g. of 2-chloro-12-ethyl-3-methyl-12H-quinoxalino- [2,3-b1phenoxazine from Example 6 in 90 ml. of dry toluene is heated to 90 C. 5 g. of dimethyl sulfate is added over a period of 15 minutes. The reaction mixture is stirred at 90 C. for 45 minutes, then cooled to 25 C. and filtered, The precipitate is washed with cold toluene, then With diethyl ether and vacuum dried. The methosulfate quaternary thus formed dyes acrylic fibers blue-violet shades With excellent properties.

Example 8 A mixture of 4.52 g. of l0-methyl-3-hydroxy-2-phenazinone, 2.91 g. of oaminophenol and 25 ml. of 3-picoline is heated to gentle reflux and stirred at the boil for 3 hours. The reaction mixture is then cooled and filtered, and the precipitate washed with water. The precipitate is then slurried in warm 1% sodium hydroxide solution, filtered at 60 C., washed with water until alkali free and dried at 60 C. The product, 12-methyl-12H-quinoxalino-[2,3-b1phenoxazine, dyes acrylic fibers blue-violet shades with excellent fastness properties and has the formula:

r N a 7 8 Example 9 Example 11 3.05 g. of 3-hydroxy-10-methyl-7-sulfamoyl-2-phen- 4.8 g. of 9,l2-dimethyl-l2H-quinoxalino[2,3-b]pheazinone and 2 g. of 2-amino-4chloro-5-methylphenol are noxazine, prepared according to the procedures described reacted according to the procedure described in Example above, in 25 ml. of diethyl sulfate is stirred at 90 C. 4 except that stirring at 175 C. to 185 C. is continued for 2 hours. The reaction mixture is drowned in a large for 4 hours. The product, 2-chloro-3,l2-dimethyl-9-sulexcess of diethyl ether, filtered, and the filter cake thorfamoyl-l2H-quinoxaline-[2,3-b1phenoxazine, dyes acrylic oughly washed with ether. The product is dried at 60 C.

fibers blue-violet shades and has the structure: The quaternary ethosulfate dyes acrylic fibers violet CH3 shades with good fastness properties.

| The compounds and cations described in the examples 01 of the following table are prepared according to the procedure employed in the preceding examples. The ap- HZNO S CH3 propriate phenazinone and the appropriate o-amino- N 0 phenol or o-aminonaphthol are reacted to yield the novel Example 10 15 compounds of the invention which, when treated with an alkylating agent, yield the novel cations of the inven- The reaction is carried out exactly as Example 5 tion. The compositions of the table correspond to the except using 2.54 grams of l0-ethyl-3-hydroxy-7-methylgeneral formula 2-phenazinone instead of 2.64 grams of l0-butyl-3-hydroxy-2-phenaz1none. The product obtained dyes acryllc R2 11 13 1 R4 fibers in fast blue shades. The color 1s a more greenlsh- N N blue than the dye of Example 5. It has the structure: l 2 R5 NW N R s 6 5 4 R The color wen in each of the examples below reters CH3 a N to the color of the dyes on acrylic textile materials.

(R01, R R R R R Color None H 9-CH; H H H BlueViolet. None 9-CH 2-Cl D0. --CH3 H Q-CHz 2-Cl H H D0. None H Q-CH; 2-NO: H H Violet. CH H 9-CH 2-N0g H H D0 None H 9-0 H H 3-NO1 H Red-Violet -CH H 9'CH3 H 3-N0a H Do. None H 9-CH; H 3-CF H Do. C2H5 H Q-CHa H 3-CF3 H D0. None H 9-CH3 2-Cl 3-01 4-01 Violet. -C2H H Q-OH; 2-Cl 3-01 4-01 Do. None H 9-CH; H R; and RB combined at Blue.

3 and 4 pos. represent CH= CHGH=CH C1H5 H Q-CH; H R and R combined at Do.

3 and 4 pos. represent CH=CHCH= CH- None H 9-CH; H R and R5 combined at De.

2 and 3 pos. represent -CH= CHCH=CH -C1H H 9-CH@ H R5 and R0 combined at D0.

2 and 3 pos. represent CH=CHCH=CH -C;H H 9-CH; R4 and R5 combined at H Do.

1 and 2 pos. represent H=CHCH=CH- -benzyl H H 2-N0; H H Red-Violet. None H QCH 2-Cl 3-CH3 H B lue-Violet. None H H 2-N0a H H Red-Violet. CH3 H H H 3-NO2 H Do. None H H Z-NH; H H Blue-Violet. CH H H Q-NH: H H Do. None H H 2-0 F H H Red-Violet. CH H H H 3-013; H Do. None H H 2-Ol 3-01 4-01 Violet. 37 -C4H9(n) None H H H R and R6 combined at Blue.

3 and 4 pos. represent -CH=CHCH=CH- 38 C4Ha(n) None H H H R and R5 combined at D0.

2 and 3 pos. represent -CH=CH-CH=CH -C4Hg(11) None H H R4 and R5 combined at H De.

1 and 2 pos. represent -CH=CH-OH= CH- C1H5 None H H Z-CrHr H H Blue-Violet. C2H5 Benzyl H H 2-OuH H H D0. -C2H5 None H H H 3-SO2CH3 H Violet. --CzH5 CH H H H 3-SO2OH H Do. -CH None H H 2-Cl 3-GH H Do. C2H5 None H H 2-SO2NH2 H D0- -C:H5 None H H H 3-COC5H H Blue-Violet -C zH5 None H Q-S OaNH: H H H Violet. -(1so)C H CH; H 9-SOzNH1 H H H Do. C2 5 None H Q-SOZNH] 22-01 H H D0. OH; -CH; H Q-SOQNH: 2-Cl 3-CH H Do. -C;H5 None H 9-SO1NH: Z-CF; H H Bluish-Red. -C2H5 None H Q-SOzNHg 3'S02OH3 H H Red-Violet. -Q5H5 None H Q-CF; H H H Violet. -(1s0)C He CzH5 H Q-CF; H H H Do. QzH None H 9-0 CH H H H Do. (1so)OaHa C Hu H Q-OCH; H H H D0. -CzH None H Q-OCH; 2-Cl H H Blue-Violet. -C2H5 CH H Q-OOH; 2-Cl H H Do. OH None H 9-CH; Z-CH; H H Do.

Example R (B ),1 R R R R R Color None R1 and R combined at H H H Blue.

9 and 10 pos. represent -CH= CHCH=CH- CH Ru and R3 combined at H H H D0.

9 and 10 pos. represent -CH= CHCH=OH None R1 and R3 combined at H H H Do.

8 and 9 pos. represent CH= CHCH= CH- None H Q-NO: H H H Red-Violet. None H 9-NH2 H H H Blue-Violet. None H 9-SONH 2-Cl 3-CH; H Violet. None H 9-CF3 2-Cl 3-Cl 4-Cl Red-Violet None H Q-SOzCH; 2Cl 3-Cl 4-Cl Do. None H Q'SOZOHQ 2-Cl 3 CH3 H Violet. None H 90 OH; 2-Cl 3-CH3 H Blue-Violet. None H 9-O CH3 2 11 H H Beddish-Blue. None H Q-NHOQH; H H H Do. CH H H H H 4-NHC H Blue-Violet. None 11-0 0 OH; H H H H Violet. None -CH H H H H Blue-Violet.

The compounds and cations of the invention can be used for dyeing acrylic and modacrylic polymer fibers, yarns and fabrics giving fast red-violet to blue shades when applied thereto by conventional dye methods. Acrylic textile materials are those which consist of at least 85% acrylonitrile and modacrylic textile materials are those consisting of at least 35% but less than 85 acrylonitrile. The compounds and cations of the invention also give excellent dyeings on acid-modified acrylic textile materials such as the sulfonate modified acrylic fibers described in U.S. Patents 2,837,500, 2,837,501 and 3,043,811. The novel compounds and cations can also be used to dye the sulfonate modified polyester fibers described in U.S. Patent 3,018,272. Examples of the textile materials that are dyed with the compounds and cations of the invention are those sold under the tradenames Orlon, Orlon 42, Verel, Acrilan, Dyrel, Creslan and Dacron 64. In general, the compounds and cations exhibit improved fastness, for example, to washing, to alkaline perspiration, gas (atmospheric fumes) and sublimation.

As described above, the 12-alkylquinoxalophenoxazine compounds and cations of the invention are characterized by a structure which is distinct from other compounds. This distinctive structure imparts unexpected properties to the present dyes, especially when they are used as dyes for dyeing acrylic and modacrylic textile materials, including aifinity for acrylic fibers, and satisfactory brightness and fastness to light. Thus, We have found the compounds of the invention to possess excellent fastness properties when used as dyes on acrylic and modacrylic textile materials when such dyeings are tested by methods such as described in the A.A.T.C.C. Technical Manual, 1965 edition.

Textile materials dyed by the compounds and cations of the invention are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 65-5% of vinyl pyridine units as described in U.S. Patents 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified by 655% of vinylpyrrolidone units, for example, as described by U.S. Patent 2,970,783, or modified with 65-5% acrylic ester or acrylamide units as described in U.S. Patents 2,879,253, 2,879,254 and 2,838,470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of the copolymers readily dyeable with the dyes of the invention are the modacrylic polymers such as described in U.S. Patent 2,831,826 composed of a mixture of (A) 70-95% by weight of a copolymer of from 30 to 65% by weight of vinylidene chloride or vinyl chloride and 7035% by weight of acrylonitrile, and (B) 305% by weight of a second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula 0 R CH:=(3( iN wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least 50% by weight of :at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

Another type of modacrylic polymer that can be dyed with the compounds and cations of the invention is an acetone soluble mixture of (A) 95% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 305% by weight of an acrylamide homopolymer having the above formula wherein R R and R are as described above. Specific polymers of that type contain 7095% by weight of (A) a copolymer of from 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30-5% by weight of a lower N- alkylacrylamide polymer such as poly-N-methacrylamide, poly-N-isopropylacrylamide and poly N tertiarybutylacrylamide.

The following example illustrates one way in which the compounds of the invention can be used to dye acrylonitrile polymer textile material.

Example An amount of 0.1 gram of dye is dissolved by warming in 5 cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. Five cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and, in the case of Orlon 42 acrylic textile material, the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A composition of matter having the formula 11 wherein R represents lower alkyl;

R represents lower alkyl or benzyl;

X represents o-phenylene, lower alkyl-o-phenylene,

lower alkoxy-o-phenylene, halo-o-phenylene, cyanoo-phenylene, lower alkylsulfonyl-o-phenylene, carbamoyl-o-phenylene, lower alkylcarbamoyl-o-phenylene, hydroxy-o-phenylene, lower alkanoyl-o-phenylene, lower alkoxycarbonyl-o-phenylene, sulfamoylo-phenylene, lower alkylsulfamoyl-o-phenylene, lower alkylsulfonamido o phenylene, thiocyanato-ophenylene, trifluoromethyl o phenylene amino-ophenylene, [phenyl-o phenylene, benzoyl-o-phenylene,] phenylamino-o-phenylene, or, when Y represents an o-phenylene group, o-naphthylene;

Y represents o-naphthylene or an o-phenylene group having the formula wherein R represents hydrogen or halogen;

R represents hydrogen, lower alkyl, lower alkoxy, halogen, lower alkanoylamino, nitro, cyano lower alkylsulfonyl, carbamoyl, lower alkylcarbarnoyl, hydroxy, lower alkanoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfonyl, lower alkylsulfonamido, thiocyanato, trifluoromethyl, amino, phenyl, benzoyl, or phenylamino; and

R represents hydrogen or halogen; and

Z represents a monovalent acid anion selected from the group consisting of lower alkylsulfate, halogen, ptoluenesulfonate, and benzenesulfonate.

2. A composition of matter as defined in claim 1 wherein R represents lower alkyl;

X represents an o-phenylene group of the formula wherein R represents hydrogen, sulfamoyl, lower alkylsulfonyl, trifluoromethyl, lower alkyl, halogen or lower alkoxy; and Y represents o-naphthylene or an o-phenylene group of the formula wherein R represents hydrogen, lower alkyl, trifiuoromethyl, halogen, nitro, sulfamoyl, or lower alkylsulfonyl. 3. A composition of matter as defined in claim 1 wherein R represents lower alkyl; X represents o-phenylene;

and Y represents o-phenylene or naphthylene.

4. A composition of matter as defined in claim I having the formula (E2115 5 \/W ITI// OL/ .0113 Z 5. A composition of matter as defined in claim I having the formula 6. A composition of matter as defined in claim I having the formula \N7 0/ CH;

' (III-Ia Z 7. A composition of matter as defined in claim 1 having the formula vol. 27, pp. 7789 Berlin, Springer, 1937.

Diepolder Berichte vol. 32, pp. 3520-8 Relied on Kehrmann et al. I Chem. Abst. vol. 21, pp. 743-4 1927).

Kehrmann et a1. II Helv. Chim. Act. vol. 8, pp. 16-20 (1925).

Yuasa Chem. Abst. vol. 48, Column 12900 (1954).

H R. JILES, Primary Examiner N. TROUSOF, Assistant Examiner US. Cl. X.R.

P0-105U UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5, 5, 32 Da December EL 1969 Inventor) Raymond C. Harris and James M, Stralev I: is certified that error appears in the above-identified parent and that said Letters Patent are hereby corrected as shown below:

Claim 1, Column 10, lines 68 through 74, the formula should read:

Claim 1, Column 11, line 15, cancel [phen 3 l-o-phenylene,

benzoyl-o-phenyl-" and line 14, cancel ene,]"

.u ..'-.ALED 1 2 1971 U Am mama 11. mm In Amnin Officer mm 1:. :m.

00.188101!!! 0! EMS 

